Fluorinated esters with a pesticide action

ABSTRACT

Described are fluorinated aromatic compounds of the formula: WHEREIN N 0 OR &gt; OR = 1 AND M 0, 1 OR 2; WHEN N 0, M 0 OR 1; WHEN N 1, M 0, 1 OR 2; WHEN N &gt; 1, m 0; and A. WHEN N 0, M 0, X may be alkyl with a linear or branched chain, alkoxyl, hydroxyl, phenyl optionally substituted, nitro, halo, carboxy-2-fluoro-ethyl and acyl; B. WHEN N 0, M 1, X and Y equal or different from each other, may be alkyl with a linear or branched chain, alkoxyl, hydroxyl, phenyl optionally substituted, nitro, halo, acyl; C. WHEN N 1, M 0, X may be cyclohexyl, phenyl, optionally substituted, benzyl, benzoyl, azophenyl; D. WHEN N 1, M 1 OR 2, X and Y, the same or different from each other, may be nitro or halo; E. WHEN N &gt; 1; M 0, X may be halo, alkoxyl, phenyl optionally substituted.

United States Patent Rossi et al.

[451 Sept. 5, 1972 [54] FLUORINATED ESTERS WITH A PESTICIDE ACTION [73] Assignee: Montecatini Edison S. P. A., Milan.

. Italy [22] Filed: Nov. 15, 1968 [21] Appl. No.: 776,274

[30] Foreign Application Priority Data Nov. 16, 1967 Italy ..22760 A/67 [52] US. Cl ..260/469, 260/207.1, 260/47] R, 260/473 R, 260/475 F, 260/476 R, 260/474,

[51] Int. Cl. ..A01n 9/24, C070 69/76, C07c 69/78 [5 8] Field of Search ..260/469 [56] References Cited UNITED STATES PATENTS 3,436,418 4/ 1969 Tonelli et al ..260/469 Primary ExaminerLorraine A. Weinberger Assistant Examiner-R. S. Weissberg Att0rneyCurt M. Avery, Arthur E. Wilfond, Herbert L. Lerner and Daniel J. Tick [5 7] ABSTRACT Described are fluorinated aromatic compounds of the formula:

wherein n=0 or 3 l and m =0, l or 2; when n =0, m=0or l;whenn=l,m=0, l or2;whenN l,m 0; and

a. when n O, m O, X may be alkyl with a linear or branched chain, alkoxyl, hydroxyl, phenyl optionally substituted, nitro, halo, carboxy-2-fluoroethyl and acyl;

b. when n O, m l, X and Y equal or different from each other, may be alkyl with a linear or branched chain, alkoxyl, hydroxyl, phenyl optionally substituted, nitro, halo, acyl;

c. when n l, m 0, X maybe cyclohexyl, phenyl,

optionally substituted, benzyl, benzoyl, azopheny d. when n= l,m=l or 2, X and Y, the same ordifferent from each other, may be nitro or halo;

e. when n 1; m 0, X may be halo, alkoxyl,

phenyl optionally substituted.

4 Claims, No Drawings FLUORINATED ESTERS WITH A HESTICIDE ACTION U.S. patent application Ser. No. 416,919, filed Dec. 8, 1964 and now US. Pat. No. 3,436,418, describes a class of compounds of the formula:

R 2),. 2)2 in which m is zero or 1, n is zero or 1 and more precisely, when n 1, R is a phenyl (optionally substituted by a halogen, preferably chlorine, OCH and N0 diphenyl or naphthyl; while when m n 0, R is a styryl, a mercaptotolyl or diphenylmethyl.

The above compounds are effective against plant pests and more particularly are effective against summer and winter eggs of mites. The effectiveness against the latter is the particular aspect of their range of action as pesticides.

We have now surprisingly found that among numerous other esters of fluoroethyl alcohol, having a pesticide action, there are a few similar ones which are not within the above formula, which are, however, endowed with characteristics particularly suited for practical use. These compounds just form the object of the invention.

An object of this invention are also the compositions which contain said compounds as active principles and their use for the disinfestation of plants from plant parasites. The new compounds fall within the formula:

wherein n=0or z 1 and m=0, l or 2;when n=0, m =Oor l;whenn= l,m=0, 1 or2;whenn 1,m=0; and

a. when n 0, m 0, X may be alkyl with a linear or branched chain, alkoxyl, hydroxyl, phenyl optionally substituted, nitro, halo, carboxy-2-fluoroethyl and acyl;

b. when n 0, m l, X and Y equal or different from each other, may be alkyl with a linear or branched chain, alkoxyl, hydroxyl, phenyl optionally substituted, nitro, halo, acyl;

0. when n 1, m O, X may be cyclohexyl, phenyl, optionally substituted, benzyl, benzoyl, azophenyl;

d. whenn= 1, m=1 or 2, X and Y, the same ordifferent from each other, may be nitro or halo;

e. when n l; m 0, X may be halo, alkoxyl, phenyl optionally substituted.

A further object of this invention is the use of B- fluoroethyl-benzoate against mites and their winter eggs. We have prepared esters of fluoroethyl alcohol with varying structures in which was ascertained a pesticide action, but only those comprised by the above-cited general formula are unforeseeably provided with such kind of characteristics as to suggest that they may be conveniently used for the disinfestation of plants.

Among the esters examined there were:

a phenyl-zx-mercapto acetate of B- fluoroethyl liquid b.p. 9799C at 0.2 mm Hg fl-fluoroelhyl-laurate B-fluoroethyl-phenylsuccinate a-phenylsulfon-a-phenylacetate a-(p-chlorophenylsulfon)-aphenylacetate of fi-fluoroethyl B-fluoroethyl p benzoylaminophenyl-acetate B-fluoroethyl nicotinate B-fluoroethyl pmethoxyphenylacetate ,B-fluoroethyl 2,4dinitro-phenylacetate fi-fluoroethyl-p-methoxybenzoate B-fluoroethyl p-nitrobenzoate fl-fluoroethyl ester of the Zphenanthrylacetic acid B-fluoroethyl ester of 3- phenanthrylacetic acid ,B-fluoroethyl phenylmercaptoacetate B-fluoroethyl phenylsulfonacetate p-chlorophenylmercaptoacetate of B-fluoroethyl p-chlorophenylsulfonacetate of B- fluoroethyl fl-naphthylmercaptoacetate of B- fluoroethyl fi-naphthylsulphonacetate of [3- fluoroethyl a-naphthylmercaptoacetate of B fluoroethyl 9-anthranylmercaptoacetate of B- fluoroethyl a-naphthylsulfonacetate of B- fluoroethyl p-cyclohexylphenylacetate of [3- fluoroethyl fif1uoroethyl-tetralylacetate fifluoroethyl ester of 01 hromophenylylacetic acid fi-fluoroethyl p-phenylendiacetate fi-fluoroethyl 4-ethylphenylacetate B-fluoroethyl fl-B- dimethylbutyrate B-fluoroethyl norbornylacetate B-fluoroethyl p-tolylacetate fl-fluoroethyl ester of 3,4-

dichlorophenylacetic acid B-fluoroethyl pbenzoylphenylacetate B-fluoroethyl pacetylphenylacetate at 0.05 mm Hg oil b.p. 9799C at 0.01 mm Hg liquid b.p. 135-137C at 0.1 mm Hg XX from EtOH m.p. 119-1 19.5C

XX from EtOH m.p. l02.5l03.5C

oil b.p. til-84C at 0.1 mm Hg liquid b.p. l99207C at 0,1 mm Hg liquid b.p. 97-98C at0.()l mm/Hg waxy solid m.p. 3539C Kp 146-148C oil b.p. l05l()6C at 0.05 mm Hg XX from benzene m.p. 7375C XX from ethylacetate m.p. 154157C liquid b.p. 133-135C at 15 mm Hg liquid b.p. 102-103C at 0.05 mm Hg XX from MeOH, m.p. 5758C liquid b.p. 98-100C at 0.1 mm Hg XX from EtOH, m.p. 59.5-6lC solid, m.p. 50-52C b.p. 157-160C at 0.05 mm Hg oil, b.p. 177-180C at 0.05 mm Hg liquid, b.p, 103-106C at 0.1 mm Hg XX from EtOH, m.p. 43-44C viscous liquid b.p. 113-115C at 0.05 mm Hg XX from EtOH, m.p. 4243C viscous oil, b.p. l52l54C at 0.05 mm Hg XX from EtOH, m.p. of 76C viscous oil, b.p. 144-147C at 0.05 mm Hg XX from ligroin, m.p. 55-56C viscous oil, b.p. 187-193C at 0.1 mm Hg yellow oil, E 135-140C oil, E 121-123C raw solid, m.p. Gil-67C m.p. 5354C and E 167-170C liquid, E 92C liquid, E 9698C liquid, E 3945C liquid, E 8()82C liquid, E 92-94C liquid, E 108-1 12C XX from ligroin m.p. 7072C B-fluoroethyl macetylphenylacetate B-fluoroethyl 4-phenylbenzoate B-fluoroethyl 2,4-

dinitrophenylacetate B-fluoroethyl p(p-nitrophenoxy) phenylacetate B-fluoroethyl oquinolylacetate l3-fluoroethyl pmethylmercaptophenylacetate B-fluoroethyl p-rnethylsulfonylphenylacetate B-fluoroethyl ester of p(achlorobenzyl) benzoic acid B-fluoroethyl p-phenylmercaptophenylacetate B-fluoroethyl N-phthaloylaminoacetate B-fluoroethyl pbenzylphenylacetate B-fluoroethyl pphenylazophenylacetate B-fluoroethyl p(N-benzylidenamine) phenylacetate B-fluoroethyl B 4-diphenylacrylate B-fluoroethyl B-benzoylpropionate B-fluoroethyl B(4-diphenylyl) propanoate B-fluoroethyl ester of undecenoic acid B-fluoroethyl 3(p-phenylbenzoyl) propanoate fl-fluoroethyl pbromophenylacetate B-fluoroethyl benzoate B-fluoroethyl 2,4,5-

trichlorophenylacetate fi-fluoroethyl p chlorophenylacetate B-fluoroethyl pfluorophenylacetate B-fluoroethyl o-nitrobenzoate B-fluoroethyl o-benzoylbenzoate B-fluoroethyl o-chlorobenzoate B-fluoroethyl 4-tert.-butylbenzoate B fluoroethyl 3-5-dinitrobenzoate B-fluoroethyl salicylate B-fluoroethyl terephthalate fl-lluoroethyl p-( p-bromophenyl) phenylacetate B-fluoroethyl (p-chlorophenyl)butyrrate B-fluoroethyl (p-methoxyphenyl)butyrrate liquid, E 130l35C XX from petroleum ether m.p. 67-68C E 175-1s0c XX from petroleum ether m.p. 7678C liquid, E l5ll53C XX from hexane m.p. 52.554C

XX from EtOH m.p. 77-70C XX from MeOl-l, m.p. 1l3-1l5C XX from hexane, m.p. 74-76C liquid, E l67-l69C XX from ligroin,

m.p. 85-87C oil, E 150C liquid, E 8284C XX from MeOl-l, m.p. lO3-IO5 solid, E 1 -1 C liquid, E 92-96C liquid, E,, 89-92C liquid, E l l7l20C di XX from ethylacetate/ petroleum ether, m.p. 62-63C liquid, E, 8 l-84C q uro: 9598C di XX from ethylacetate/ petroleum ether m.p. 80-8lC q on-0.2 66-67C di XX from ethylether/ ligroin m.p. 89-90C di XX from MeOH m.p. 6870C In the above table, XX stands for crystals.

Among the preferred compounds of the invention are the B-fluoroethyl ester of 4-diphenylyl carboxylic acid, the B-fluoroethyl ester of B-(4-diphenylyl) propionic acid, the B-fluoroethyl ester of p-cyclohexylphenylacetic acid, the B-fluoroethyl ester of benzoic acid, the ,Bfluoroethyl ester of methoxybenzoic acid, the B-fluoroethyl ester of 'y( 4-diphenyl)butyric acid.

In so far as practical use is concerned, the most relevant characteristic of these compounds, which are also endowed with a pesticide effect, is their effectiveness in destroying the mite eggs, even those eggs belonging strains resistant to the currently used products.

In order to fully realize the practical importance of the data reported further on, it is necessary that in evaluating the ovicidal (egg-killing) action of a product, one must keep in mind that it is necessary to distinguish whether the product is active against the summer eggs or against the winter eggs. As a matter of fact, it is well known that some mite species hibernate in the state of eggs. These latter are less attackable by pesticidal agents than are the summer eggs, particularly due to the greater obstacle to penetration of the pesticide substance represented by the corium of the winter egg. The control of the winter mite eggs offers many advantages. However, in order to achieve good results against this kind of eggs by means of products of common use (e.g.: mineral oils admixed with parathion) it is necessary to act immediately at the resumption of the vegetative activity and with the most timely intervention. This, however, is often hampered by adverse atmospheric conditions while, on the other hand, many phytotoxic effects may be furthermore provoked if the treatment is carried out at an advanced vegetative stage of the plant.

Quite obviously, the treatment in deep winter does not cause such troubles and besides one also avoids injury to numerous species of useful insects (predatory insects and parasites) as well as eliminates the risks connected with the persistence on the plants of the residues of the substances used for the treatments, since often enough these substances show a rather strong toxicity for warm-blooded animals. Furthermore, from a practical point of view, the possibility to carry out the control of mites during the winter, that is, in a period when the workers in the fruit'growing farm are less occupied, represents an undoubted advantage. The treatments in full winter may be carried out with mineral oils, with oils boosted with the admixture thereto of synthetic active substances. This meets negligible success because of the particular, already previously mentioned, resistance of the hibernating eggs.

We have now surprisingly found that the compounds of the present invention are not only effective against the summer eggs of the acari, but are also very active against their winter eggs with treatments carried out in deep winter. Furthermore, they are also quite effective against the other vital stages of the mites and against psyllids, insects which start their egg-laying in winter. Their effectiveness attains such high limits as to ensure a total disinfestation of the parasites and displays, at the same time, a considerable persistence of action. This actually means that said compounds unfold their action for a long time after their spraying onto the plants. The greater persistence of the action of a pesticide agent allows one to reduce the number of treatments and makes the disinfestation safer and more complete. Thus, we have here a characteristic of the greatest importance from the practical point of view.

From what has been stated, it appears quite evident that the chief object of this invention is to provide means particularly effective and useful for the disinfestation of plants from winter eggs of mites and from some insect species, while a secondary object is that of providing means which, with the action against the winter eggs, also combine the activity against the other vital stages of mites so as to form complete overall fighting means against these pests.

wherein X, Y, n and m have the above-mentioned meaning, with fi-fluoroethyl alcohol, by using the means of the prior art. In general, one prefers to esterify in the presence of an acid catalyst and of a solvent, not mixahle with water, which forms an azeotropic mixture with the latter to keep the reactants in solution and allow the removal of the water by distillation as it forms during the esterification. Some of the compounds may be prepared by taking advantage of the so-called transesterification, that is, by treating an ester of the acid involved with fl-fluoroethyl alcohol.

The preparation of compounds and formulations containing as active principles the substances of this invention does not offer any difficulties since they are soluble in many of the commonly used solvents. Depending on the specific use to which they are intended, formulations of different types may be prepared: Powder formulations are prepared by thoroughly mixing the active substance with inert fillers and diluents such as kaolin, talc, attapulgite, sepiolite, diatomaceous earth, artificial silicates, etc.

By thoroughly mixing together the active substance with inert powders (as above) and with a substance or mixture of substances with a surfactant or wetting action, which may be chosen, for instance, from the classes of condensates of ethylene oxide with alkylphenols or with higher aliphatic alcohols or from the class of calcium or sodium alkylbenzene (naphthalene) sulfonates, so-called wettable powders are prepared. That is, formulations are obtained which can be added to water for giving suspensions that are used for disinfestation by spraying.

Liquid formulations emulsifiable in water are prepared by adding to a solution of the active substance in a solvent, insoluble in water, a substance or mixture of substances with a surfactant or wetting action, which may belong to the classes previously listed.

By adding the formulations of this type to water, one obtains emulsions ready for use. Liquid formulations based on mineral oils combined with emulsifying surfacting agents and co-solvents, containing the substance of this invention, are conveniently used, when dispersed in water, for treatment of plants infested by parasites.

The proportions or ratios between the active substance and the other components of the formulations may vary within wide limits. In order to more clearly illustrate this invention, examples for the preparation will be given, provided with data on the pesticidal activity, it being understood that these examples are not to be construed as in any way limiting the protective scope of the invention itself.

The following thus illustrates the technique of the tests on the activity of most of the products. In reporting the data obtained, the possible variants introduced into this technique will be also specified.

in order to carry out the biological activity tests, a formulation was used which was prepared by dissolving 20 parts by weight of the product under examination in parts by weight of xylol, adding to the solution 5 parts of a mixture of equal parts of calcium dodecylbenzosulfonate and of a condensate of ethylene oxide with nonylphenol. Thereupon, the quantity of formulation necessary for obtaining the desired concentration of active substance was admixed to the water under stirring. The emulsions thus obtained were sprayed onto the plants or on those parts of the plants which were infested by parasites.

The tests were carried out on the following mite species: TETRANYCHUS URTICAE, strain: Sambucus sensitive to the phosphoorganic products, to ovicides and to bis-parachlorodiphenylcarbinols (strain kindly supplied by Dr. W. Helle, of the Laboratorium voor Toegepaste Entomologie van de Universiteit van Amsterdam-Limnaeus Straat 28); T 515 (strain kindly supplied by: Dr. W. Helle of the University of Amsterdam, as specified above) which is highly resistant against Tedion, but not to phosphoorganic compounds; Baardse (strain kindly supplied by Dr. W. Helle), which is polyresistant, i.e. resistant against phosphoorganic substances, to Tedion and a little to Kelthane; Panonychus ulmi, strain resistant to the (R) phosphoorganic compounds; Eotetranychus carpini vitis in the adult stage and in the stage of summer eggs; and on some insect species.

In the case of Panonychus ulmi tests were carried out also on winter eggs. The methods for determining the activity of the pesticides were as follows:

The acaricide (adult mites) activity was established by direct spraying onto discs of leaves infested with female mites and preserved at 2426C on wetted cotton in open Petridishes, and recording the mortality after 24 hours.

The direct ovicidal activity was determined by infesting the leaf-discs with 100 adult females. After 24 hours, the females were removed and the discs with the eggs were sprayed with the aqueous emulsion containing the active substance and were then stored as described above until a few days after the hatching of the untreated control eggs.

The ovicidal activity due to the residual effect was determined by spraying discs made from leaves with the aqueous emulsion of the active substance. After 2 hours, females were transferred onto these leaves and were left to lay eggs on the treated surface of said leaves. After 24 hours the females were removed and the percentage of unhatched eggs was calculated after the hatching of the eggs laid on non-treated discs (control discs).

The assessing or determining of the activity against winter eggs was carried out under natural environment conditions according to the following procedures:

Apple trees in pots, placed under natural environment conditions, strongly and uniformly infested with winter eggs of Panonychus ulmi of a FAG-resistant strain, bred in a laboratory, were sprayed before their vegetative awakening February-March). During the hatching period of the eggs, various successive samplings were carried out on the new vegetation, until reaching at the end of the hatching, the complete defoliation of the plants in order to count the number of present larvae. In this way it was possible to calculate the percentage reduction of the infestation on the treated plants in comparison to the control plants. For each repetition one single plant was considered.

The tests of adulticide action persistence were carried out by spray treating small apple trees in pots with aqueous dispersions of the products under examina- M 2875 Summer eggs Adults Winter eggs,

percent Direct, percent Residual, percent Direct, percent Residual, percent Biglogicalactivity 0.01 0.1 0.01 0.1 0.01 0.1 0.01 0.1 0.01 0.1 i

Tetranychus urticae Sambucus Tetra'nychus urticae T 515. Tetnmychus urticae Baard Panonychus ulmi R 1 Eotetranychus carpim' F. uitia fabae I Pear Psylla larvae tion.. These plants were 'tiiiikb'fin ih'op'e'n 01102? '7 natural environmental conditions. At different intervals of time after the initial treatment, small discs were drawn from the leaves. These discs were then infested in the laboratory, each with 100 females. The mortality of the latter was then checked after 24 hours.

EXAMPLE NO. 1

. The mixture was then refluxed until complete elimination of the water. The whole mixture was then cooled 40 down and 1 1.5 g of B-fluoroethanol I 24 g of 4-diphenyl-carboxylic acid were added.

The mixture was then refluxed until the water was removed. The mass was then cooled and water was added. By filtering, part of the non-esterified acid was eliminated (about 11 g). The organic phase was then washed with diluted solution of sodium hydroxide, then with water again and finally was dried on anhydrous 50 CaSO and evaporated under reduced pressure. A residue of 12 g of solid substance was obtained. A sample of this substance, purified by crystallization from petroleum ether, is a white crystalline substance with melting point from 67-68C, and is the B-fluoroethyl ester of 4-diphenylcarboxylic acid.

Analysis:

calculated F 7.78%

EXAMPLE NO. 2 of B-(4-diphenyl)-propionic acid; M

fluoroethyl ester 2939 Into a 500 cc flask, provided with a stirrer, a thermometer and a Marcusson device for the distillation of water present in the form of an azeotropic mixture, were charged:

150 cc of benzene l 1.6 g of monohydrated p-toluenesulfonic acid. The whole was then reflux heated until complete elimination of the water. The mass was then cooled down and 7.7 g of B-fluoroethanol and 14 g of [3-(4diphenyl)-propionic acid were added.

The whole mixture was then refluxed until the water was eliminated. The organic phase was, thereupon, washed with a dilute sodium hydroxide solution, then again with water and finally was dried on anhydrous CaSO, and evaporated under reduced pressure. Thereby 13.5 g of an oily substance were obtained as a residue. This substance, purified by distillation under reduced pressure (E l50l5lC), is a colorless liquid which, after a certain period, completely solidifies, and is the fluoroethyl ester of B-(4-diphenyl)- propionic acid.

The analysis showed:

calculated F=6.98%

found F 6.62%

CHz-CIIz-C o O-CHzCIIr-F found F 7.45% M 2030 Winter eggs,

percent Summer eggs Adults Direct, percent Residual, percent Direct, percent Residual, percent Biological activity 0. 01 0. 1 0.01 0.1 0. Ol 0.1 0.01 0.1 0.01 0. l

Tetmnychus urticae Sambuous 100 100 J8 100 81 100 6 100 Tetranychus urticae T 616 100 100 96 100 48 100 8 71 Tetranychus urticue Baardse. 91 100 8 100 31 100 5 Panonychus ulmi R- 1 5 100 92 100 100 100 100 100 81 100 Eotetra'nychus carpini F 100 100 100 100 07 100 Aphisfabae Macrosiphum solam'. 100 100 Aspidiotus hedarae v 100 100 Pear Psylla larvae EXAMPLE NO. 3

B-fluoroethyl ester of the p-(p-bromophenyl)phenylacetic acid; M 3060 Into a 500 cc flask, provided with a stirrer, a thermometer and a Marcusson device for the distillation of the water in the form of an azeotropic mixture, were charged:

160 cc of benzene 1 1.2 g of p-toluenesulfonic acid 19 g of p-(p-bromophenyl)phenylacetic acid 8.4 g of B-fluoroethanol at 95% The whole was then reflux heated until complete elimination of the water. Thereupon the mixture was washed in an organic solution first with water, then with a 2 percent solution of NaOH and again twice with water. The whole was then dried on anhydrous CaCl filtered and evaporated under reduced pressure. As a solid residue there remains 22 g of a greasy brown product. A sample of this substance, purified by crystallization from methanol and recrystallized from the same solvent, is a yellow crystalline substance of melting point 6870C, and constitutes the B- fluoroethyl ester of p-(p-bromophenyl)phenylacetic 200 cc of benzene g of monohydrated p-toluenesulfonic acid. The mixture was then reflux heated until complete elimination of the water. It was then cooled down and added thereto were:

16.7 g of B-chloroethanol 32 g of 'y-(4-diphenyl )butyric acid. Thereupon, the mixture was refluxed thereby eliminating the reaction water. The whole was then cooled down and water was again added to it. The organic phase was then washed with a diluted solution of sodium hydroxide, again washed with water and finally dried on anhydrous CaCl and evaporated under reduced pressure. A residue of 35 g of a semisolid substance was obtained which, when subjected to distillation under reduced pressure (E l60-l 62C), yielded 29 g of a colorless low melting substance constituting ,B-fluoroethyl ester of y-(4-diphenyl)butyric acid. The analysis showed:

calculated F 6.64% found F=6.66%

acid, 25 ontolnorrt-coocmcrm Biological Winter eggs Summer eggs Adults Activity: direct direct Tetranychus I00 I00 I2 85 3O urticae Panonychus 89.8 99.9 61 I00 33 I00 ulmi R strain M 2942 Summer eggs Adults Winter eggs,

percent Direct, percent Residual, percent Direct, percent Residual, percent Biological activity 0. 01 0. 1 0. 01 0. 1 0. 01 0. 1 0. 01 0. 1 0. 01 0. 1

Tetranychus urticae Sambucus 73 100 9 47 Tetnmychus urticae T 515 30 100 4 21 Tetra'nychus urticae Baardae 12 95 3 24 Panonychus ulmi R 100 100 27 100 Eotetranychus carpini F. Mm. 100 100 88 100 Aphz'sfabae 7 99 Macrosiphum solani g 3 Aspidiotus hederae 78 Fear Psylla larvae J6 99.6

The analysis showed: E A PLE N 5 calculated F 5.63% found F 5.55%% X M O calcula'ed fmnd EH23 50 B-fluoroethyl ester of p-cyclohexylphenylacetic acid;

C I F M 2769 E 0 0 CI Into a 250 cc flask provided with a stirrer, a thermometer and a Marcusson device for distilling water in the form of an azeotropic mixture, were charged: 100 cc of benzene 25.5 g of monohydrated p-toluenesulfonic acid. The mixture was then heated at reflux until complete elimination of the water. The whole was then cooled down and added thereto were: 1 1.2 g of B-fluoroethanol B! M 3060 EXAMPLE NO. 4

29 g of p-cyclohexyl-phenylacetic acid. The whole was then refluxed thereby eliminating the reaction water. The mixture was then cooled down and water was again added to it. The organic phase was then washed with a diluted solution of sodium bicarbonate, then again with water, thereupon it was dried on anhydrous CaSO and finally evaporated under reduced pressure. A residue of 35 g of an oily substance C O O-CHrCH 1" EXAMPLE NO. 7

f O O-CHZCHH' B-fluoroethyl ester of p-methoxybcnzoic acid; M 2478 Into a 500 cc flask provided with a stirrer, a thermometer and a Marcusson device forv the distillation of water in the form of an azeotropic mixture, were I charged:

150 cc of benzene 33.5 g of p-methoxybenzoic acid 37.9 g of p-toluenesulfonic acid M 2700 27.5 g of B-fluoroethanol at 90%.

Summer eggs Adults Winter eggs,

percent Direct, percent Residual, percent Direct, percent Residual, percent Biological activity 0. 01 0. 1 0. 01 0. 1 0. 01 0. 1 O. 01 0. 1 0. O1 0. l

Teiranychus um'cae Sambucus 100 100 91 100 92 Tetranychus urticae T 616 100 100 85 100 67 Telranychus urticae Baardse. 100 100 59 95 40 Panonychus ulmi 100 87 100 .18 100 76 Eoteiram chua carpini F. 100 100 100 Aphisfabae. 79 lllacrosz'phum solam'; 92 Aspidiotus /l8d6Tl18 98 Pear Psylla larvae EXAMPLE NO. 6

B-fluoroethyl ester of salicylic acid; M 3056 Into a 500 cc flask provided with a stirrer, a thermometer and a Marcusson device for distilling water in the form of an azeotropic mixture, were charged:

150 cc of benzene 27.6 g of salicylic acid 34.4 g of p-toluenesulfonic acid 17.8 g of B-fluoroethanol at 95%. This mixture was refluxed until complete elimination of the reaction water. The whole was then cooled down and water was added thereto. A part of the nonesterified acid (about 15 g) was filtered off; The organic phase was thereupon washed with a dilute solution of sodium carbonate, then again washed with water and finally dried on CaCl and evaporated under reduced pressure. 12 g of an oily substance were thereby obtained as a residue. A sample of this substance, subjected-to distillation under reduced pressure (E 6667C), is a colorless oil consisting of the ,B-fluoroethyl ester of salicylic acid.

calculated F= 10.31% foundF= 10.11%

The mixture was then refluxed until complete elimination of the reaction water. The whole was then cooled down and water was added to it. Thereupon, part of the non-esterified acid (about 19 g) was eliminated by filtration. The organic phase was then washed with a dilute solution of sodium carbonate, again washed with water, dried on CaCl and finally evaporated under reduced pressure. 15 g of an oily substance were obtained as a residue. A sample of this substance, subjected to distillation under reduced pressure (E 98l 00C), is a colorless oil constituting B-fluoroethyl ester of p-methoxybenzoic acid.

Analysis gave:

B-fluoroethyl ester of p-nitrobenzoic acid; M 2479 Into a 500 cc flask provided with a stirrer, a thermometer and a Marcusson device for distilling water in the form of an azeotropic mixture, were charged:

150 cc of benzene 36.7 g of p-nitrobenzoic acid 37.9 g of p-toluenesulfonic acid 27.5 g of B-fluoroethanol at 90% The mixture was then reflux heated until complete elimination of the reaction water. The whole was then cooled down and water was added to it. The organic phase was washed with a dilute solution of sodium carbonate, then again with water and finally was dried on CaCl and evaporated under reduced pressure. A residue of 42 g of a solid substance was obtained. A sample of this substance, purified by crystallization first from ligroin and then from ethanol, is a white crystalline substance with melting point 58.559.5C, constituting B-fluoroethyl ester of p-nitrobenzoic acid.

Analysis: 7

calculated F 8.91% found F 8.58%

EXAMPLE NO. 9

B-fluoroethyl ester of 3,5-dinitrobenzoic acid; M 3050.

Into a 500 cc flask provided with a stirrer, a thermometer and a Marcusson device for distilling water in the form of an azeotropic mixture, were charged:

150 cc of benzene 42.4 g of 3,5-dinitrobenzoic acid 34.4 g of p-toluenesulfonic acid 17.8 g of fl-fluoroethanol at 95%. The whole mixture was then reflux heated until complete elimination of the reaction water. This mass was then cooled down and water added to it. The benzenic phase was, thereupon, washed with a dilute solution of sodium carbonate, then again with water and finally it was dried on CaCl and vaporized under reduced pressure. A residue of 49 g of a solid substance was obtained. A sample of this substance, purified by crystallization from ethyl acetate and from petroleum ether, is a white crystalline substance with a melting point between and 81C, constituting B-fluoroethyl ester of 3,5-dinitrobenzoic acid. Analysis:

calculated F 7.35%

EXAMPLE NO. 10

B-fluoroethyl ester of p-benzylphenylacetic acid; M 2884 Into a 500 cc flask provided with a stirrer, a thermometer and a Marcusson device for distilling water in the form of an azeotropic mixture, were charged:

200 cc of benzene 22.6 g of p-toluenesulfonic acid 27.9 g of p-benzylphenylacetic acid 12.8 g of B-fluoroethanol at The whole mixture was then refluxed until complete elimination of the reaction water. Thereupon, the mixture was cooled down and was added thereto. The organic phase was then washed with a dilute solution of sodium bicarbonate and then again washed with water, dried on anhydrous CaSO and evaporated at reduced pressure. A residue of 34 g of an oily substance was obtained. This substance was then distilled under reduced pressure (E =l58C) to give 25 g of a colorless oil, constituting B-fluoroethyl ester of p-benzylphenylacetic acid. Analysis:

calculated F 6.98%

found F= 6.32%

CHzC O OCHzCHgF EXAMPLE NO. 1 1

fi-fluoroethyl ester of 4-tert-butylbenzoic acid; M 3053 Into a 500 cc flask provided with a stirrer, a thermometer and a Marcusson device for distillation of water in the form of an azeotropic mixture were charged:

150 cc of benzene 35.6 g of p-terbutylbenzoic acid 34.4 g of p-toluenesulfonic acid 17.8 g of B-fluoroethanol at 95%. This mixture was refluxed until complete elimination of the reaction water. Thereupon the whole was cooled down and new water was added thereto. The organic phase was then washed with a dilute solution of sodium carbonate, then again with water and finally was dried on CaCl and evaporated under reduced pressure. 44 g of a semisolid oily substance was obtained as a residue. By filtration the solid part, constituting about 5 g of non-esterified acid, was then removed. A sample of this substance, subjected to distillation under reduced pressure (E 9598C), is a colorless oil constituting the fl-fluoroethyl ester of 4-tert-butylbenz0ic acid. Analysis:

calculated F 8.47%

found F 8.20%

COOCH2CH2F HaC-C|CH3 CH M 3053 Biological Winter eggs Summer eggs Adults Activity: v direct direct Tetranychus urticae 100 100 45 100 Panonychus ulmi R 90.3 98.1 100 100 100 100 EXAMPLE NO. 12

B-fluoroethyl ester of p-phenylazophenylacetic acid; M 2921 Into a 500 cc flask provided with a stirrer, a thermometer and a Marcusson device for distilling water in the form of an azeotropic mixture, were charged:

200 cc of benzene 20.2 g of p-toluenesulfonic acid 30 g of p-phenylazophenylacetic acid 1 1.5 g of B-fluoroethanol at 95% This mixture was then refluxed until complete elimination of the reaction water. The whole was then cooled down and the benzenic phase was separated from a pitchy clot that had formed during the reaction. Thereupon the organic solution was washed with water, then with a dilute solution of sodium bicarbonate and finally again with water. The mixture was then dried on anhydrous CaSO and evaporated under reduced pressure. 19 g of a solid substance remained as a residue. A sample of this substance was extracted with n-hexane at 60C. The orange-red crystalline substance obtained had a melting point of from 7476C, constituting B- fluoroethyl ester of p-phcnylazophcnylacetic acid. Analysis:

calculated F 6.64%

found F 6.37%

(I1II UOOCII UH I" Biological Activity:

Winter eggs Summer eggs Adults direct direct 0.0l%0.1% 0.01%0.1% 0.01% 0.1%

Tetranychus urlicae Sambucus 88 92 8 91 Pano- I nychus ulmi R 65.7 97.7 58 93 37 98 EXAMPLE NO. 13

B-fluoroethyl ester of p-chlorobenzoic acid; M 3051 Into a 500 cc flask provided with a stirrer, a thermometer and a Marcusson device for distilling water in the form of an azeotropic mixture, were charged:

100 cc of benzene 23.5 g of p-chlorobenzoic acid 25.8 g of p-toluenesulfonic acid 15.1 g of B-fluoroethanol at The mixture was then refluxed until complete elimination of the reaction water. The whole was then cooled down and water was again added to it. Thereupon part of the non-esterified acid (about 5 g) was removed by filtration. The organic phase was then washed with a dilute solution of sodium carbonate, again with water and finally dried on CaCl and evaporated under reduced pressure. A residue of 22 g of an oily substance was obtained. A sample of this oily substance, subjected to distillation under reduced pressure (E 8 l-83C) yields a colorless oil constituting B- fluoroethyl ester of p-chlorobenzoic acid. Analysis: Y

calculated F 9.37%

found F 9.10%

I 17 1s Biological Winter eggs sungner 88 2 reflux rate was regulated in relation to the temperature lrect irect Activity: 0014170196 0.01% 01% of the column top. Once the methanol fraction had been removed, the excess fluoromethanol was distilled under reduced pressure, thereby obtaining a residue 1 h usifaz us 100 0 49 100 constituting 75 g of solid substance. A sample, purified Pmwwyvhw by crystallization from ethanol and subsequently from ulmi R 68.1 99.8 100 100 100 100 ligroin, gives a colorless crystalline substance with a melting point of from 89 to 90C, constituting EXAMPLE NO. 14 fluoroethylester of terephthalic acid.

B-fluoroethyl ester of benzoic acid; M 2856 i 'i' ted l 4 710/ into a 500 cc flask provided with a stirrer, a ther- 32 1 3 0 mometer and a Marcusson device for distilling water in the form of an azeotropic mixture, were charged:

120 cc ofbenzene 34.4 g of p-toluenesulfonic acid 24.4 g of benzoic acid 17.5 g of B-fluoroethanol at 95%.

The whole mixture was then reflux heated until complete elimination of the reaction water. The mixcoo-o Hr-CHrF M 3051 ture was then cooled down and water was added to it. The organic phase was then washed with a dilute solu- Blological Winter eggs Summer eggs Adults tion of sodium carbonate, then again with water and Activity, direct finally was dried on anhydrous CaCl and evaporated 00% 01% 091% 01% 001% 01% under reduced pressure. 29.5 g of a liquid substance were obtained as a residue. The mixture was then sub Te anychus jected to distillation under reduced pressure (E ZZZZ 61-63C) whereby 21 g of a colorless liquid were obulmi R 98.3 99.5 100 100 100 100 tained, constituting the B-fluoroethyl ester of benzoic acid. Analysis: EXAMPLE NO. 16

calculated F 1 1 .29%

found F=10-98% B-fluoroethyl ester of 2,4,5-trichlorophenylacetic acid;

M2957 (l3OOCH;CH2F 24 g of 2,4,5-trichlorophenylacetic acid in 150 cc benzene were esterified with 8.3 g of fluoroethanol in 1. the presence of 19 g of p.toluenesulfonic acid through the azeotropic removal of the reaction water. After M 2856 cooling down, the reaction mixture was poured into water. The organic phase that separated was then Rioiogical washed with a dilute solution of sodium hydroxide and C(IVI 2 winter eggs Summer eggs Mum then with water. After drying on anhydrous CaSO,, the

( solvent was evaporated ofi under reduced pressure. 19

direct direct 0.01% 0.1% 001% 01% 0.01% 01% g of liquid substance were obtained as a residue. A sam ple, purified by distillation under reduced pressure (E 1 10-l15C) constitutes a colorless, low-melting substance of B-fluoroethyl ester of 2,4,5- trichlorophenylacetic acid.

Sambucus 99 100 3 I00 A l i f gf calculated F= 6.66%

ulim' R 100 100 97 100 28 100 fo nd F 52% CHz-C U C.H1F The activity test was carried out according to the already described technique of operating in the laboratory on detached twigs of an apple 55 tree.

EXAMPLE NO. 15

B-fluoroethylester of terephthalic acid: M 3051 2957 g of methylester of terephthalic acid and 1 15.2 g 60 of fluoroethanol were mixed together with 2 g of ptoluenesulfonic acid in 500 cc flask provided with a gg'fii' eggs 'f f g t net; We filled-type rectifying column. The column was provided y 0.01% 0.1% 0.01% 0.1% 0.01% 0.1%

with a device for refluxing and with a distilling cooler. The reaction mixture was heated gradually to reach 5 mmnych,

boiling point at room pressure and the methanol was z 100 89 100 then made to distill, keeping an adequate reflux, as the R 100 100 96 98 m0 100 methanol forms in the course of the reaction. The

We claim:

1. The compound having the formula:

ooocaHm 2. The compound having the formula:

3. The compound having the formula:

CHZC 0 0 C2114]? 

2. The compound having the formula:
 3. The compound having the formula:
 4. The compound having the formula: 